JPH0489870A - Reactive dye composition and method of dyeing fibrous material by using the same - Google Patents

Abstract

PURPOSE:To form a yellow reactive dye composition which is suitable for dyeing particularly cellulosic fibrous material and gives a dyed article having good fastness and free from discoloration by mixing two specified dyes. CONSTITUTION:A reactive dye composition containing a dye of formula I in free acid form and a dye of formula II in free acid form, the amount of the latter being 0.5 to 3.5 times that of the former by weight. In formula I, X1 and X2 are each independently a hydrogen atom, alkyl, etc.; R1 and R2 are each independently a hydrogen atom or optionally substituted alkyl ; X is halogen or an optionally substituted pyridinio group; (m) is an integer of 1 to 8; Y is a hydrogen atom, a group of formula III (wherein A is phenyl or naphthyl; Z is CH=CH2, etc.; (l) is 0 or 1), etc. In formula II, D is alkyl, phenyl substituted by alkoxy, etc., or naphthyl substituted by two or eight sulfo groups; X3 and X4 are each independently a hydrogen atom, a sulfo group, etc.; (n) is 0 or 1; Z1 is CH=CH2, etc.; Q is a sulfo group, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a reactive dye suitable for dyeing textile materials, in particular cellulosic fiber materials or textile materials containing cellulose fibers, which provides fast and non-discoloring dyeings. Regarding the composition.

[Conventional technology]

Reactive dyes for dyeing cellulosic fiber materials or IiA fiber materials containing cellulose fibers are required to have excellent various properties such as level dyeing, fastness, and reproducibility. Generally, as yellow reactive dyes, azobenzene dyes are often used because they have excellent build-up properties, light fastness, sweat/sunlight fastness, chlorine fastness, washability, and amm seismic intensity.

[Problem that the invention is trying to solve]

However, dyed products obtained using commercially available azobenzene-based yellow reactive dyes as three primary color components exhibit a so-called photochromism phenomenon in which the dyes return to a deep color when irradiated with strong light energy. For example, there is a problem that the hue of a dyed product differs when viewed in a bright place and in a dark place, and in the same dyed product, there are areas that are exposed to strong light and areas that are in the shadow that are less exposed to light. This causes problems such as different hues. Furthermore, azobenzene-based color reactive dyes do not have sufficient heat fastness, and there is a problem that the dyes fade due to drying of dyed products or high-temperature treatments such as ironing. It also causes a decrease in dye concentration during dyeing (180'C).

[Means to solve the problem]

The present inventors have conducted extensive studies with the aim of finding a yellow reactive dye that is suitable for dyeing textile materials, particularly cellulose-based fiber materials or textile materials containing cellulose-based fiber materials, and that provides dyed products with no photochromism and good heat resistance. As a result, the inventors discovered that a reactive dye composition containing a specific dye met the objectives and completed the present invention.

That is, the present invention provides compounds of the following general formula (I) u in the form of free acids [wherein Xl and Xl are each independently a hydrogen atom, an alkyl group, an alkoxy group, an acylamino group, or a ureido group, and R1 and Rg are each independently represents a hydrogen atom or an optionally substituted alkyl group, X represents a halogen atom or an optionally substituted pyridinio group, m represents an integer of 1 to 8, Y represents a hydrogen atom, the following formula (1) % formula )(1) (wherein, human is an optionally substituted phenyl or naphthyl group, 2 is -CH=CHg or -CHtCH*Z
21 represents a group that is eliminated by the action of an alkali, and 1 represents Ol or 1. ), or a group represented by the following formula (2) [wherein D is a phenyl group substituted with at least 1 ml selected from an alkyl group, an alkoxy group, a phenoxy group, a sulfo group and an acylamino group, or 2 or 8 sulfo groups (in the formula, Xs, Xt, Rt, Ri
, X and m have the above meanings, and W represents an aromatic or aliphatic divalent group. ) represents a group represented by ] In the form of a dye represented by and 0.5 to 8.5 times its weight of free acid, the following general formula 0 koxy group, n is 0 or 1, zl represents -CH=Cut or -CRxCH2Zt', Z+ ' represents a group that is eliminated by the action of an alkali. Q is a sulfo group or the following formula (8) (wherein Rs and R4 are each independently a hydrogen atom or an optionally substituted alkyl group, Xs is a halogen atom or a pyridinio group, Yl is a hydrogen atom or the following formula (4) ) % Formula % (4) (In the formula, AI is an optionally substituted phenylene or naphthylene group, 2! is -CH=CHg or -CMICH
! Z! z and I represent a group that can be eliminated by the action of an alkali. ) represents a group represented by ) represents a group represented by However, what if Q represents a sulfo group? ! In represents 1, and when Q represents a group represented by formula (8), in
represents O, and a method for dyeing a fiber material characterized by using the reactive dye composition.

In the general formula α), examples of the alkyl group and alkoxy group represented by XI and Examples include. The alkyl group represented by R1 and R1 is C1
-04 alkyl group is exemplified. When Y represents a group represented by formula (1), A is a C1-C4 alkyl group, C1-C4 alkyl group,
A phenyl group which may be substituted with a C4 alkoxy group etc., Z l! -CM=C)it t f= l!
-CHgCH20SOsH1 take b K-CHtCHt
O8OsH is preferable, X is a halogen atom such as fluorine or chlorine, particularly a chlorine atom, Xl is a ureido group, Xl is a hydrogen atom, and m is preferably 2t or 8. The pyridinio group represented by X is carboxy, carbamoyl,
It may be substituted with sulfo, etc. Among these, carboxypyridinio group is particularly preferred.

Examples of the aromatic divalent group represented by W include phenylene, diphenylene, or naphthylene, which may be substituted with a substituent such as a methyl group, a chlorine atom, a methoxy group, a carboxylic acid group, or a sulfo group. It will be done. Examples of aliphatic divalent groups represented by W are preferably aliphatic groups having at least 2 m carbon atoms, especially ethylene, 1:2-propylene, 1:8 propylene, 1:
Examples include 4-butylene, ethylaminoethylene and hexamethylene.

These dyes represented by the general formula (I) used in the present invention are disclosed in JP-A-56-15481 and JP-A-56-1.
No. 40185, No. 58-186682 and No. 57-1
It can be easily produced by the method described in No. 21057 and the like.

In the above General 2〇, the phenyl group represented by D is:
Cs~C4 with methyl, ethyl, methoxy, ethoxy
Alkyl group, Cl-C4 alkoxy group, phenoxy group,
It is substituted with at least one substituent selected from the group consisting of a sulfo group and an acylamino group such as acetylamino, propionylamino, maleinylamino, and succinylamino. The alkyl group and alkoxy group represented by Xs and X4 include C1 to C4 alkyl groups such as methyl, ethyl, methoxy, and ethoxy;
An example is a C4 alkoxy group. When Q represents a group represented by formula (3), D is a naphthyl group substituted with two or a sulfo group of BOA, Xs is an alkoxy group such as methoxy, X4 is a sulfo group, Xs is fluorine, chlorine, etc. A halogen atom, especially a chlorine atom, is preferred, and formula (4)
In the group represented by, A1 is a 01-C4 alkyl group, C
A phenylene group optionally substituted with a 1-C4 alkoxy group, z! is -CH=CHt t or -CHgCH
gO8OaM, especially -CHgCHgO8OiH
It's so nice. Moreover, when Q represents a sulfo group,
D is a phenylene group substituted with 01-C4 alkyl or 01-C4 alkoxy such as methyl and methoxy;
Xs is a Ct-C4 alkoxy group such as methoxy, X4 is a C1-C4 alkyl group such as methyl, Z1 bar CH=C
Hg t Taha-CHgCH! O8OmH1 separation,
-CHgCHgO8OsH is preferred.

These dyes represented by the general formula (1) used in the present invention are disclosed in Japanese Patent Application Laid-open Nos. 61-155469 and 52-90.
268, No. 62-241968 and No. 59-1997
It can be easily produced by the method described in No. 68, etc.

The reactive dye composition of the present invention contains the dye represented by the general formula (I) and 0.5 to 8.5 times the weight of the dye, preferably 1 to 8.5 times the weight of the dye.
It can be obtained by mixing 2.5 times the weight of the dye represented by the above general formula.

In the present invention, the method of mixing reactive dyes is not particularly limited, but they may be mixed in advance before being used for dyeing, or may be mixed during dyeing.

In order to obtain a desired color tone, the reactive dye composition of the present invention
If necessary, it can be used in combination with a red component and/or a blue component. Further, there are no restrictions on the red component and the blue component, and known reactive dyes can be used. For example, as the red component, C, 1, Reactive Re
d 195 etc. is suitable, and as a blue component,
C,1, Reactive Blue 221, etc. are suitable.

The reactive dye composition of the present invention may contain, if necessary, an inorganic salt such as anhydrous mirabilite or common salt, a dispersant, a dust scattering preventive agent, a pH buffering agent,
It may contain water softeners such as polyphosphates and other known dyeing aids.

The fiber material, particularly the cellulose fiber material, in the present invention is not particularly limited, but natural or regenerated cellulose fibers such as cotton, linen, hemp, jute, ramie fiber, viscose human silk, and Bemperg are exemplified. Ru. In addition, as fiber materials containing cellulose am,
Examples include cotton/polyester blended products.

The dyeing method in the present invention may be any known method, but in the exhaust dyeing method, known inorganic neutral salts such as anhydrous sodium sulfate and common salt, and sodium carbonate, chlorinated sodium carbonate, caustic soda, sodium triphosphate, etc. Examples include a method of dyeing using a known acid binder alone or in combination, but the dyeing aid is not limited to these. There are no restrictions on the amount of inorganic neutral salt or acid binder used at this time, but at least 1
f/4 or more is preferable, and 100 fI/1 or more may be used. Further, these inorganic neutral salts and acid binders may be added to the dye bath all at once, or may be added in portions according to a conventional method. In addition, dyeing aids such as a level dyeing agent, a slow dyeing agent, and a bath softener may be used in combination by a known method, but the dyeing aids are not particularly limited to these. Also, the dyeing temperature is usually 40 to 90°C, preferably 40°C.
~70°C.

In the cold rose bud dyeing method, the dye is padded with known inorganic neutral salts such as anhydrous sodium sulfate and common salt, and known acid binders such as caustic soda and sodium silicate, and then left in a sealed packaging material at a constant temperature. A method of dyeing is exemplified. In the continuous dyeing method, a known acid binder such as caustic soda, soda carbonate, or bicarbonate soda is mixed with a dye padding solution, and after padding by a known method, dyeing is performed by dry heat or steam heat. Examples include a two-bath bagging method in which the dye is padded with a known inorganic neutral salt such as mirabilite or common salt, and a known acid binder such as caustic soda or sodium silicate, and then dyed by dry heat or steam heat using a known method. However, the dyeing method is not limited to these.

According to the present invention, it is possible not only to obtain a dyed product free from photochromism and having good heat fastness, but also to obtain a dyed product having excellent build-up properties and chlorine fastness.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. still,
In the example, the middle part indicates the Xt part, and the part indicates the heavy t96.

Example 1 40 parts of azobenzene yellow dye represented by formula (1) in free acid form and 60 parts of acetoacetanilide yellow dye represented by formula (2) in free acid form were mixed in a conventional manner. , a reactive dye composition was obtained.

The resulting reactive dye compositions were 1.5 mm and C, I.

Reactive Red 195 red dye 0.8 phantom and C,I.

Reactive Blue 221 blue dye 0.8
# was dissolved in warm water using a known method.

A 100# knitted fabric made of cotton fibers was set in a Wins dyeing device, the bath ratio was 1:15, the water temperature was 60° C., and the previously dissolved dye solution was poured into the bath by a known method. Thereafter, the knitted fabric was treated at this temperature for 20 minutes, and 15 times of soda carbonate was added to the bath using a known method. Next, the knitted fabric was treated at this temperature for 60 minutes to complete the dyeing. The obtained dyed product was washed and finished in a conventional manner. The dyed product obtained was a uniform deep olive color without photochromism. The heat fastness and chlorine fastness of the obtained dyed product were both good.

Example 2 A knitted fabric of 100 pieces made of rayon embroidery was set in a low bath ratio jet dyeing machine, and the bath ratio was set to 1:6 and the water temperature was set to 60°C.

Azobenzene yellow dye 0.5# represented by formula (1) described in Example 1 in pre-dissolved form and acetoacetanilide represented by formula (8) in pre-dissolved free acid form Yellow dye 1.0% and pre-dissolved C, 1. Reactive Re
d195 red dye 0.8 # and pre-dissolved C
, 1. After putting 0.8 # of blue dye of Reactive Blue 221 and 20 # of anhydrous sodium sulfate into the bath using a known method, the knitted fabric was treated at this temperature for 20 minutes, and 10 # of sodium carbonate was added into the bath using a known method. I put it in.

Next, the knitted fabric was treated at this temperature for 40 minutes to complete the dyeing. The obtained dyed product was washed and finished in a conventional manner. The dyed product obtained was a uniform olive color without photochromism. The heat fastness and chlorine fastness of the obtained dyed product were both good.

Example 8 A thread of 100# made of cotton fiber was set in a cheese dyeing machine,
The bath ratio was 1:10 and the water temperature was 66°C.

Formula (1) in the form of the free acid described in Example 1 previously dissolved
The following formula (4) was completed with 0.5 kg of the azobenzene yellow dye represented by and the free acid dissolved in advance. The obtained dyed yarn was washed and finished using a conventional method. The obtained dyed yarn had a uniform khaki color without photochromism. The heat fastness and chlorine fastness of the obtained dyed product were both good.

Example 4 1.0 cup of acetoacetanilide yellow dye represented by the formula (5) in the form of free acid, and pre-dissolved Saseta C.1, Reactive Red
195 red dye 0.8λ and pre-dissolved C
, I, Reactive Blue 221 blue dye 0.8 # and 80 kg of common salt were put into the bath by a known method, the yarn was treated at this temperature for 80 minutes, and the yarn was treated with 10 to 9 parts tribasic sodium phosphate by a known method. was put into the bath.

The yarn was then treated at this temperature for 60 minutes, and 40 parts of the azobenzene yellow dye shown in dyeing was added with 60 parts of the acetoacetanilide yellow dye of formula (2) in the form of the free acid described in Example 1. were mixed in a conventional manner to obtain a reactive dye composition.

The resulting reactive dye compositions 15F and C,I.

Reactive Red 195 red dye 31.
and C,1,Reactive Blue 221
blue dye 8F was dissolved in hot water and cooled to 25°C.

To this, 82.5% caustic soda aqueous solution 15-1 and 50%
Immediately after adding Baume water glass 150F and further adding water to bring the total volume to 1 liter at 25°C, this liquid was used as a padding liquid to pad a cotton fabric. The padded cotton fabric was rolled up, sealed with a polyethylene film and left at room temperature of 25° C. for 20 hours, and then the dyed fabric was washed and finished in a conventional manner. The dyed product obtained was a uniform olive color without photochromism. The heat fastness and chlorine fastness of the obtained dyed product were both good.

Example 5 70 parts of the acetoacetanilide yellow dye represented by the formula (2) in the free acid form described in Example 1 was added to 80 parts of the tenzene yellow dye represented by the formula (6) in the form of a free acid. were mixed in a conventional manner to obtain a reactive dye composition.

The obtained reactive dye composition 15f and C,I.

Reactive Red 195 red dye B,
Of, and C, 1, Reactive Blue 2
21 blue dye 8f was dissolved in hot water and cooled to 25°C. To this, sodium alginate IF, 10 f1 of sodium metanitrobenzethyl sulfonate, and 2 sodium bicarbonate.
Immediately after adding 0f and further adding water to bring the total volume to 1 liter at 25°C, this liquid was used as a padding liquid to pad a cotton fabric. I made it look like puzzling. The dyed product obtained was a uniform olive color without photochromism. The heat fastness and chlorine fastness of the obtained dyed product were both good.

Example 6 A knitted fabric 100 made of cotton fibers was set in a Wince dyeing machine, and the bath ratio was 1:15 and the water temperature was 60°C.

Formula (1) in the form of the free acid described in Example 1 previously dissolved
an azobenzene-based yellow dye represented by 0.5 and an acetoacetanilide-based yellow dye 1.0 represented by formula (2) in the form of the free acid described in Example 1 dissolved in advance, and
C, 1, ReacHve Red194 red dye 0
．． 8# and C,1,ReactiveBlue 2
22 blue dye 0.8# and sulfonation degree 110%
, a condensate (sodium salt) of dimethylnaphthalenesulfonic acid and formaldehyde with an average degree of bonding of 1.8 0.5#
, and 50 g of anhydrous sodium sulfate were added to the bath using a known method, the knitted fabric was treated at this temperature for 20 minutes, and 15 g of sodium carbonate was added to the bath using a known method. Then at this temperature 6
The powder was processed for 0 minutes and the dyeing was completed. The obtained dyed product was washed and finished in a conventional manner. The dyed product obtained was a uniform gray color. The heat fastness and chlorine fastness of the obtained dyed product were both good.

Claims (2)

[Claims] (1) In the form of a free acid, the following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, X_1 and X_2 are each independently a hydrogen atom, an alkyl group, an alkoxy group, an acylamino group, or ureido group, R_1 and R_2 each independently represent a hydrogen atom or an optionally substituted alkyl group, X represents a halogen atom or an optionally substituted pyridinio group, m represents an integer from 1 to 8, and Y represents a hydrogen atom , the following formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, A is an optionally substituted phenyl or naphthyl group, Z is -CH=CH_2 or -CH_2CH_
2Z', Z' represents a group that is eliminated by the action of an alkali, and l represents 0 or 1. ), or the group represented by the following formula (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) (In the formula, X_1, X_2, R_1, R_2, X and m
has the above meaning, and W represents an aromatic or aliphatic divalent group. ) represents a group represented by ] The following general formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (II) [In the formula, D is an alkyl group] , a phenyl group substituted with at least one selected from an alkoxy group, a phenoxy group, a sulfo group and an acylamino group, or a naphthyl group substituted with two or three sulfo groups, X_3 and X_4 are each independently hydrogen atom, sulfo group, alkyl group or alkoxy group, n is 0 or 1, Z_1 represents -CH=CH_2 or -CH_2CH_2Z_1', and Z_1' represents a group that is eliminated by the action of an alkali. Q is a sulfo group or the following formula (3) ▲ Numerical formula, chemical formula, table, etc. ▼ (3) {In the formula, R_3 and R_4 are each independently a hydrogen atom or an optionally substituted alkyl group, and X_5 is a halogen atom or pyridinio group, Y_1 is a hydrogen atom or the following formula (4) -A_1-SO_2Z_2 (4) (wherein A_1 is an optionally substituted phenylene or naphthylene group, Z_2 is -CH=CH_2 or -CH
_2CH_2Z_2', and Z_2' represents a group that can be eliminated by the action of an alkali. ) represents a group represented by } represents a group represented by. However, when Q represents a sulfo group, n represents 1, and when Q represents a group represented by formula (3), n represents 0. ] A reactive dye composition comprising a dye represented by: (2) A method for dyeing fiber materials, which comprises using the reactive dye composition according to claim 1.